Novel reactive dyes and use thereof for dyeing substrates containing nucleophilic groups

ABSTRACT

The present invention relates to novel reactive dyes of the formula (I)  
                 
 
     where R 1  to R 4  are independently hydrogen, C 1 -C 8 -alkyl, C 2 -C 8 -alkyl, wherein nonadjacent CH 2  groups may be replaced by oxygen atoms or imino or C 1 -C 4 -alkylimino groups and/or CH 2  groups by carbonyl groups, C 2 -C 8 -alkenyl, aryl, arylalkylene or a moiety containing a reactive group or the precursor of a reactive group, with the proviso that at least one of R 1  to R 4  is a moiety which contains a reactive group or the precursor of a reactive group. The present invention further relates to the use of the reactive dyes of the formula (I) for dyeing substrates containing nucleophilic groups and to preparations containing at least one reactive dye of the formula (I).

DESCRIPTION

[0001] The present invention relates to novel reactive dyes of theformula I

[0002] where R¹ to R⁴ are independently hydrogen, C₁₋C₈₋alkyl,C₂₋C₈₋alkyl, wherein nonadjacent CH₂ groups may be replaced by oxygenatoms or imino or C₁₋C₄₋alkylimino groups and/or CH₂ groups by carbonylgroups, C₂-C₈-alkenyl, aryl or a moiety containing a reactive group orthe precursor of a reactive group,

[0003] with the proviso that at least one of R¹ to R⁴ is a moiety whichcontains a reactive group or the precursor of a reactive group.

[0004] The present invention further relates to the use of the reactivedyes of the formula I for dyeing substrates containing nucleophilicgroups and to preparations containing at least one reactive dye of theformula I.

[0005] Reactive dyes have been extensively described for dyeing a widevariety of substrates. For example, the use of reactive dyes for dyeingnitrogenous fibers, such as wool, is known from U.S. Pat. No. 4,066,638,EP 107 614, EP 559 617, DE 34 41 273 and DE 21 54 942.

[0006] U.S. Pat. No. 4,102,641 discloses the use of halotriazinylreactive dyes for dyeing hair.

[0007] JP 75 025 529 A recites dye formulations for use as hair dyes.The reactive dyes used therein are based onp-sulfa-toethylsulfonylaniline as a diazo component and as afiber-reactive radical.

[0008] It is an object of the present invention to provide furtherreactive dyes which exhibit good adhesion to the substrates to be dyedand can be applied under gentle dyeing conditions.

[0009] We have found that this object is achieved by the reactive dyesof the general formula I described at the beginning.

[0010] When R¹ to R⁴ represent radicals having acidic hydrogen atoms,the reactive dyes of the formula I will ordinarily be present inprotonated form. But it will be appreciated that the reactive dyes canalso occur in the form of their—preferably physiologicallyacceptable—salts.

[0011] In the latter case, suitable cations are derived especially frommetal or ammonium ions. Metal ions are especially lithium, sodium orpotassium ions. Ammonium ions for the purposes of the present inventionare substituted or unsubstituted ammonium cations. Substituted ammoniumcations include for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl-or benzyltrialkyl-ammonium cations or cations derived from nitrogenousfive- or six-membered saturated heterocycles, such as pyrrolidinium,piperidinium, morpholinium, piperazinium or N-alkylpiperazinium cationsor their N-monoalkyl- or N,N-dialkyl-substituted products. Alkyl isgenerally straight-chain or branched C₁₋C₂₀-alkyl, which may besubstituted by 1 or 2 hydroxyl groups and/or interrupted by 1 to 4oxygen atoms in ether function.

[0012] Useful C₁-C₈-alkyl for R¹ to R⁴ includes branched or unbranchedalkyl chains, for example methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, n-octyl or 2-ethylhexyl.

[0013] Useful C₂-C₈-alkenyl for R¹ to R⁴ includes branched or unbranchedalkenyl chains, for example vinyl, propenyl, isopropenyl, 1-butenyl,2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl,2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl,1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.

[0014] C₂-C₈-Alkyl for R¹ to R⁴ in which nonadjacent CH₂ groups may bereplaced by oxygen atoms or imino or C₁₋C₄-alkylimino groups and/or CH₂groups by carbonyl groups includes for example

[0015] —(CH₂—CH₂—O—)_(p)H, —(CH₂—CH₂—O—)_(p)CH₃, —(CH₂—CH(CH₃)—O—)_(p)H,

[0016] —(CH₂₋CH₂₋NR—)_(p)H, —(CH₂₋CH₂₋NR—)_(p)CH₃ or

[0017] —(CH₂₋CH(CH₃)—NR—)_(p)H, where p is 1 or 2, or

[0018] —CH₂—O—C(═O)—[(CH₂)_(r)]H, —CH₂₋C(═O)—O—[(CH₂)_(r)]H,

[0019] —CH₂—NR—C(═O)—[(CH₂)_(r)]H and —CH₂—C(═O)—NR—[(CH₂)_(r)]H, wherer is 0, 1, 2, 3, 4 or 5, and

[0020] R is in each case hydrogen, methyl, ethyl, n-propyl, isoropyl,n-butyl, sec-butyl, isobutyl or tert-butyl.

[0021] The last-mentioned formulae include for example the radicals—CH₂—O—C(═O)—H and —CH₂—C(═O) —O—H (each with r=0), —CH₂₋O—C(═O)—CH₃ and—CH₂₋C(═O)—O—CH₃ (each with r=1) and also —CH₂₋O—C(═O)—C₂H₅ and—CH₂₋C(═O)—O—C₂H₅ (each with r=2).

[0022] The term aryl is to be understood as meaning for example phenyl,methoxyphenyl or naphthyl or aromatic rings or ring systems having 6 to18 carbon atoms in the ring system and also up to 24 further carbonatoms which may form further nonaromatic rings or ring systems having 3to 8 carbon atoms in the ring, which may each be substituted by one ormore radicals such as halogen, such as fluorine, chlorine or bromine,cyano, nitro, amino, hydroxyl, alkyl, alkoxy or other radicals.Preference is given to phenyl, p-methoxyphenyl and naphthyl.

[0023] Useful arylalkylene radicals include branched-chain orunbranched-chain phenyl-(C₁-C₅-alkylene) or naphthyl-(C₁-C₅-alkylene)radicals such as phenylmethylene, phenylethylene, phenylpropylene,phenyl-1-methylethylene, phenylbutylene, phenyl-1-methylpropylene,phenyl-2-methylpropylene, phenyl-1,1-dimethylethylene, phenylpentylene,phenyl-1-methylbutylene, phenyl-2-methylbutylene,phenyl-3-methylbutylene, phenyl-2,2-dimethylpropylene,phenyl-1-ethylpropylene, naphthylmethylene, naphthylethylene,naphthylpropylene, naphthyl-1-methylethylene, naphthylbutylene,naphthyl-1-methylpropylene, naphthyl-2-methylpropylene,naphthyl-1,1-dimethylethylene, naphthylpentylene,naphthyl-1-methylbutylene, naphthyl-2-methylbutylene,naphthyl-3-methylbutylene, naphthyl-2,2-dimethylpropylene ornaphthyl-1-ethylpropylene, and also their isomeric or stereoisomericforms. Useful aryl radicals include substituted or unsubstituted phenylor naphthyl radicals. A preferred arylalkylene radical is benzyl.

[0024] As to the meaning of R¹ to R⁴ as a moiety containing a reactivegroup or the precursor of a reactive group, there now follows someremarks. For simplicity, a moiety which contains a reactive group or theprecursor of a reactive group is here and hereinafter also referred toby the synonymous “reactive moiety”.

[0025] Additive reaction of the reactive moieties with the relevantgroups in the substrate, for example with the amino groups of hair,means that, for the vinyl sulfone group for example, the amino groups ofthe hair undergo an addition reaction with the reactive moieties as perthe following scheme:

[0026] Substitutive reaction of the reactive moieties with the relevantnucleophilic groups (HNuc—) in the substrate, for example with the aminogroups of hair, in contrast, means that, for example for thechlorotriazine group, the leaving groups or atoms (chlorine in this casefor example) in the reactive moieties are substitutively replaced by theamino groups of the hair as per the following scheme:

[0027] Additively reacting moieties for R¹ to R⁴ include for exampleacryloyl, mono-, di- or trichloroacryloyl, mono-, di- ortribromoacryloyl, —CO—CCl═CH—COOH, —CO—CH═CCl—COOH, 2-chloropropionyl,1,2-dichloropropionyl, 1,2-dibromopropionyl, 3-phenylsulfonylpropionyl,3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl,2-chloro-2,3,3-trifluorocycloutylcarbonyl,2,2,3,3-tetrafluorocyclobutylcarbonyl,2,2,3,3-tetrafluorocyclobutylsulfonyl,2-(2,2,3,3-tetrafluorocyclobutyl)acryloyl, 1- or 2-alkyl- or 1- or2-arylsulfonylacryloyl, such as 1- or 2-methylsulfonylacryloyl.

[0028] An additively reacting moiety R¹ to R⁴ which contains theprecursor of a reactive group is especially —M¹⁻SO₂₋C₂H₄Q, where M¹ isphenylene or branched or unbranched C₁₋C₈-alkylene, preferablyC₁-C₄-alkylene, wherein nonadjacent CH₂ groups may be replaced by oxygenatoms or imino or C₁₋C₄₋alkylimino groups. Examples are CH₂, (CH₂)₂,(CH₂)₃, (CH₂)₄, CH(CH₃)CH₂, CH(CH₃)CH(CH₃), (CH₂)₅, (CH₂)₆,(CH₂)₂O(CH₂)₂, (CH₂)₃O(CH₂)₂, (CH₂)₂O(CH₂)₂O(CH₂)₂, (CH₂)₂NH(CH₂)₂,(CH₂)₃NH(CH₂)₂, (CH₂)₂NH(CH₂)₂NH(CH₂)₂,

[0029] Q is an alkali-detachable group, for example chlorine, bromine,C₁₋C₄-alkylsulfonyl, phenylsulfonyl, OSO₃H, SSO₃H, OP(O) (OH)₂,C₁-C₄-alkylsulfonyloxy, phenylsulfonyloxy, C₁₋C₄-alkanoyloxy,C₁₋C₄-dialkylamino or a radical of the formula

[0030] where Z¹, Z² and Z³ are identical or different and eachindependently represent C₁₋C₄-alkyl or benzyl and each An⁻is oneequivalent of an anion. Useful anions include for example fluoride,chloride, bromide, iodide, mono-, di- or trichloroacetate,methanesulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate.

[0031] Q is preferably chlorine, acetate and SSO₃H, particularlypreferably Q is OSO₃H.

[0032] A moiety R¹ to R⁴ which contains a reactive group is inparticular —M¹⁻SO₂₋CH═CH₂, where M¹ is as defined above.

[0033] Further additively reacting moieties containing a reactive groupor the precursor of a reactive group include for example those of theformulae IIa to IIe, where U is either —C₂H₄Q, as defined above, or avinyl radical.

[0034] Substitutively reacting moieties for R¹ to R⁴ include for examplehalogen-substituted radicals derived from 1,3,5-triazine, quinoxaline,phthalazine, pyrimidine, pyridazine or 2-alkylsulfonylbenzothiazole asheterocyclic parent structure.

[0035] Of particular suitability in this context are the followingheterocyclic radicals which may each contain additively reactingsubstituents:

[0036] where each Z⁴ independently represents hydrogen, C₁₋C₆₋alkyl orphenyl,

[0037] Hal is fluorine, chlorine or bromine,

[0038] U¹ is hydrogen or nitro,

[0039] U² and U³ are independently hydrogen or C₁₋C₆₋alkyl which may besubstituted by hydroxyl, halogen, cyano, hydroxysulfonyl or a radical ofthe formula —SO₂₋U, in which case U is as defined above, and may beinterrupted by 1 or 2 nonadjacent oxygen atoms or imino orC₁₋C₄₋alkylimino groups, or

[0040] U² and U³ combine with the joining nitrogen atom to form apyrrolidinyl, piperidinyl, morpholinyl, piperazinyl orN—(C₁₋C₄₋alkyl)piperazinyl radical, or

[0041] U² is a radical of the formula

[0042] where the rings B¹ and B² may each be singly or doublyhydroxysulfonyl-substituted and/or benzofused and the ring B² mayindependently be substituted by one or two substituents selected fromthe group consisting of chlorine, nitro, C₁₋C₄₋alkyl, C₁₋C₄₋alkoxy,cyano, carboxyl, acetylamino, hydroxysulfonylmethyl, a radical of theformula CH₂₋SO₂₋U, a radical of the formula SO₂₋U, a radical of theformula NH—CO—U and a radical of the formula NU²⁻CO—NU²⁻L—SO₂₋U, where Uand U² are each as defined above and L is C₂₋C₆₋alkylene which may besubstituted by hydroxyl, chlorine, cyano, carboxyl,C₁₋C₄₋alkoxycarbonyl, C₁₋C₄₋alkanoyloxy or sulfato and may beinterrupted by 1 or 2 nonadjacent oxygen atoms, by 1 or 2 imino groupsor by 1 or 2 C₁₋C₄₋alkylimino groups. U² and U³ are each for examplemethyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or2-methylpentyl.

[0043] U² and U³ may each also be for example hydroxy-C₁₋C₄-alkyl, suchas hydroxymethyl, 1-hydroxyeth-1-yl, 2-hydroxyeth-1-yl,1-hydroxyprop-1-yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl,1-hydroxyprop-2-yl, 2-hydroxyprop-2-yl, 1-hydroxbut-1-yl,2-hydroxybut-1-yl, 3-hydroxybut-1-yl, 4-hydroxybut-1-yl,1-hydroxybut-2-yl, 2-hydroxybut-2-yl, 1-hydroxybut-3-yl,2-hydroxybut-3-yl, 1-hydroxy-2-methylprop-3-yl,2-hydroxy-2-methylprop-3-yl, 3-hydroxy-2-methylprop-3-yl or2-hydroxymethylprop-2-yl.

[0044] U² and U³ may each further be for example cyanomethyl,cyanoethyl, cyanopropyl or cyanobutyl or hydroxysulfonylmethyl,2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl or 2- or4-hydroxysulfonylbutyl.

[0045] L is for example (CH₂)₂, (CH₂)₃, (CH₂)₄, CH(CH₃)CH₂,CH(CH₃)CH(CH₃), (CH₂)₅ or (CH₂)₆.

[0046] L may also be for example (CH₂)₂O(CH₂)₂, (CH₂)₃O(CH₂)₂,(CH₂)₂O(CH₂)₂O(CH₂)₂, (CH₂)₂S(CH₂)₂, (CH₂)₃S(CH₂, (CH₂)₂S(CH₂)₂S(CH₂)₂,(CH₂)₂NH(CH₂)₂, (CH₂)₃NH(CH₂)₂, (CH₂)₂NH(CH₂)₂NH(CH₂)₂,

[0047] Preferred reactive dyes according to the invention are thosewherein the substituents independently have the following meanings:

[0048] R¹ and R²:

[0049] hydrogen, C₁-C₄-alkyl;

[0050] R³: hydrogen;

[0051] R⁴: —M¹—SO₂—R⁵;

[0052] M¹ —(CH₂)n—,

[0053] R⁵: vinyl, —CH₂—CH₂—OSO₃H, —CH₂—CH₂—O—C (═O)—R⁶, —CH₂₋CH₂₋O—R⁷;

[0054] R⁶ and R⁷:

[0055] C₁-C₆-alkyl; and

[0056] n: 1 to 4.

[0057] Particularly preferred reactive dyes are compounds of the formulaI wherein the substituents independently have the following meanings:

[0058] R¹ and R²:

[0059] hydrogen and methyl;

[0060] R³: hydrogen;

[0061] R⁴: —CH₂—CH₂—SO₂—CH═CH₂, —CH₂—CH₂—SO₂—CH₂—CH₂₋OSO₃H.

[0062] The present invention further provides for the use of thereactive dyes according to the invention and their preferred embodimentsfor dyeing substrates containing nucleophilic groups.

[0063] Such substrates include for example a very wide variety of stylesof cellulose products, for example cotton-based textiles, paper fornewspaper and magazine production, pulps for hygiene purposes forexample and wood products, for example for furniture making, animalhides, for example leather, and animal furs, but also human skin, forexample for the application of temporary tattoos, and human hair.

[0064] The reactive dyes according to the invention and their preferredembodiments find preferred use for dyeing substrates containinghydroxyl, mercapto, amino and/or imino groups.

[0065] More particularly, the reactive dyes according to the inventionand their preferred embodiments find use for dyeing keratinic fibers,specifically animal or human hair.

[0066] The present invention also provides preparations containing atleast one reactive dye according to the invention.

[0067] The reactive dyes according to the invention are customarilyapplied in dissolved form. For the preferred cosmetic applications, thereactive dyes are dissolved in an aqueous cosmetically acceptablemedium. In this aqueous cosmetically acceptable medium, the pH variesbetween 5 and 9 and is preferably in the range from 6 to 8. It isadjusted to the desired value using mild inorganic or organic bases,salts of weak acids or buffers. Examples are ammonia, ammoniumcarbonate, potassium carbonate, sodium carbonate, sodium hydroxide,monoethanolamine, diethanolamine, triethanolamine, disodiumhydrogenphosphate, sodium citrate and sodium bo-rate.

[0068] The reactive dyes are present in the preparations in fractions offrom 0.01 to 10% by weight, based on the total weight of thepreparation.

[0069] Customary assistants in preparations for hair dyeing are anionic,cationic, nonionic or amphoteric surfactants or mixtures thereof.Suitable surfactants are soaps, alkylbenzenesulfonates,alkylnaphthalenesulfonates, sulfates, ether sulfates and sulfonates offatty alcohols, quaternary ammonium salts, such astrimethylcetylammonium bromide, cetylpyridinium bromide, quaternium 1 toX (INCI), cocoyltrimethylammonium methylsulfate (INCI),hydroxyethylcetyldimomium phosphate (INCI), cetyltrimethylammoniumchloride, optionally ethoxylated fatty acid ethanolamides,polyethoxylated acids, alcohols or amines, polyglycerated alcohols,polyethoxylated or polyglycerated alkylphenols and also polyethoxylatedalkyl sulfates. Surfactants are present in the compositions of theinvention in an amount from 0.5 to 40% by weight, based on the totalweight of the preparation.

[0070] Further customary assistants are organic solvents assolubilizers, eg. C₁-C₄-alcohol such as ethanol and isopropanol,glycols, glycol ethers such as ethylene glycol, propylene glycol,2-methoxyethanol, 2-ethoxyethanol or 2-butoxyethanol, and also glycerol.Solvents are generally present in an amount of 0-40% by weight, based onthe total weight of the preparation.

[0071] To simplify the handling of the preparations according to theinvention, it is customary to add. thickeners to them as assistants.Customary thickeners are cellulose derivatives such as methyl-,hydroxymethyl-, hydroxyethyl-, hydroxypropyl- orcarboxymethyl-cellulose, sodium alginate, gum arabic, xanthan gum,tragacanth, acrylic acid polymers, polyvinylpyrrolidone, vinylacetate/crotonic acid copolymers, vinyl acetate/vinylpyrrolidonecopolymers, butyl vinyl ether/maleic anhydride copolymers, methyl vinylether/maleic anhydride copolymers, or an inorganic thickener such asbentonite. These thickeners are generally used in an amount of up to 5%by weight based on the total weight of the preparation.

[0072] Hair cosmetic preparations which are to be used in the form ofgels further comprise gel-forming substances such as, for example,carbomers (INCI). For certain caring properties, the preparations mayfurther comprise cationic polymers and silicone compounds. Suitablecationic polymers are, for example, polyquaternium 1 to x (INCI),copolymers of vinylpyrrolidone/vinylimidazolium salts (Luviquat® FC,Luviquats® HM; BASF Aktiengesellschaft, Ludwigshafen), copolymers ofvinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat PQ 11); cationic cellulose derivatives(Polyquaternium-4 and 10), acrylamido copolymers (Polyquaternium-7) andcationic guar gum derivatives, eg. guar hydroxypropyltriminium chloride(INCI). Suitable silicone compounds are, for example,polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes,polyethersiloxanes or silicone resins.

[0073] Further customary assistants are mild antioxidants which do notreact with the dyes, penetrants, sequestrants, buffers, perfume oils,sunscreens (UV-A and UV-B), preservatives, hair-cleaning products andbiologically active substances such as panthenol, bisabolol andvitamins, for example of type A, C and E.

[0074] The preparations of the invention can be used in liquid form,generally thickened, as cream, paste, as gel or in some other suitableform.

[0075] The hair colouring compositions of the present invention may, inaddition to the dyes discussed herein above include other nonoxidative,oxidative and other dye materials. Optional nonoxidative and other dyessuitable for use in the hair colouring compositions and processesaccording to the present invention include demi-permanent,semi-permanent, temporary and other dyes. Non-oxidative dyesas definedherein include the so-called “direct action dyes”, metallic dyes, metalchelate dyes, fibre reactive dyes, acid dyes, basic dyes, non-ionicdyes, anionic dyes, cationic dyes, HC dyes and other synthetic andnatural dyes.

[0076] Oxidative hair colouring agents to be used in the compositionsherein are typically, but without intending to be limited thereby,oxidative hair colouring agents, consisting essentially of at least twocomponents, which are collectively referred to as dye formingintermediates (or precursors). Dye forming intermediates can react inthe presence of a suitable oxidant to form a coloured molecule. The dyeforming intermediates used in oxidative hair colorants include: aromaticdiamines, aminophenols, various heterocycles, phenbls, naphthols andtheir various diaminobenzene or its derivatives.

[0077] The hair colouring compositions may also comprise at least oneoxidising agent, which may be an inorganic or organic oxidising agent.

[0078] The oxidising agent is preferably present in the colouringcomposition at a level of from about 0.01% to about 20%, more preferablyfrom about 0.01% to about 10%, more preferably from about 1% to about 6%by weight of the composition. A preferred oxidising agent for use hereinis an inorganic peroxygen oxidising agent.

[0079] In a preferred application, a hair cosmetic preparation isapplied to the hair, allowed to act for from 5 to 50 minutes, preferablyfrom 10 to 30 minutes, and then the hair is rinsed and, if necessary,washed with a conventional shampoo.

[0080] A warm preparation or external heat can be used to speed up thedyeing or deepen the dyeing over the same treatment time. Preference isgiven to using temperatures within the range from 20 to 40° C.

[0081] The reactive dyes of the invention produce uniform dyeings andgood coverage of white hair. The dyeings are lightfast, washfast,weatherfast and rubfast.

[0082] Furthermore, reactive dyes and their alternative dyeing methodmake it possible to dispense with H₂O₂ as an oxidant in the dyeingprocess. What is particularly advantageous here is the fact that the hueis predetermined by the dye and not developed on the hair. Thissimplifies the preparation of dye mixtures and shading.

[0083] The examples hereinbelow illustrate the preparation of thecompounds according to the invention and the use thereof

PREPARATION EXAMPLE 1

[0084] a) Preparation of 2-hydroxyethyl 2′-aminoethyl sulfone:

[0085] 245 g (2.4 mol) of 96% sulfuric acid were added to 400 g of ice.484 g (4 mol) of 2-aminoethyl 2′-hydroxyethyl sulfide (J. R. Lotz, B. P.Block, W. C. Fernelius, J. Phys. Chem., 63 (1959), p. 541) were thenadded dropwise over 30 minutes while the temperature rose to 45° C. Thiswas followed by the addition of 1 g (0.004 mol) of sodium tungstate(Merck) and 10 g of citric acid (Merck), the pH was adjusted to 4.5 with20% aqueous sodium hydroxide solution and the temperature was raised to80° C. 953 g (8.4 mol) of 30% hydrogen peroxide solution were addeddropwise over 3 hours while the pH was maintained between 4.5 and 5 with20% aqueous sodium hydroxide solution. Excess peroxide was destroyedwith sodium sulfite. The solution was concentrated in a rotaryevaporator and was admixed with a total of 1 500 ml of ethanol added alittle at a time. Each addition of an ethanol portion was followed byconcentrating until finally the remaining oil was made to crystallize byaddition of 200 ml of methanol.

[0086] This yielded 775 g (3.85 mol) of 2-hydroxyethyl 2′-aminoethylsulfone.

[0087] b) Preparation ofN1-(2-(2-sulfatoethylsulfonyl)ethyl)-2-nitrobenzene-1,4-diamine

[0088] 20 g (0.128 mol) of 4-fluoro-3-nitroaniline and 50 g (0.2 mol) of2-hydroxyethyl 2′-aminoethyl sulfone were stirred up in 100 g ofsulfolane and admixed with 24 g of sodium carbonate. The reactionmixture was heated at 100° C. for 8 hours. After cooling to roomtemperature, 200 ml of concentrated sulfuric acid were added dropwiseover an hour. The temperature was kept below 25° C. by external cooling.The reaction mixture was subsequently stirred for one hour and thenadded gradually to 400 g of ice and 100 g of water. The resultantsuspension was admixed with 30 g of sodium acetate and filtered. Thefilter residue was washed with a little saturated potassium chloridesolution and then dried at 30° C. under reduced pressure to leave 30.8 gof the dye (65% of theory) having the above-indicated structure as redcrystals. UV: λ_(max) (DMF/water 1:1) 498 nm.

Dyeing Example

[0089] 1.25 g of the reactive dye of example 1 were dissolved in 25 mlof water and adjusted to pH 7 with sodium hydrogenphosphate. After thesolution had been heated to 36° C., a bleached strand of human hair (2g) was immersed in the solution for 20 minutes at 36° C. The hair wasthen rinsed with water and air dried. A deep red hair coloration wasobtained.

Formulation Examples

[0090] A) Hair Dyeing Cream

[0091] Phase I:

[0092] 1.5 g of ceteareth-6 (and) stearyl alcohol (INCI)

[0093] 1.5 g of ceteareth-25

[0094] 6.0 g of cetearyl octanoate

[0095] 3.0 g of cetearyl alcohol

[0096] Phase II:

[0097] 2 g of reactive dye of example 1

[0098] 2 g of propylene glycol

[0099] 84 g of distilled water

[0100] q.s. citric acid/triethanolamine to adjust to pH 7

[0101] q.s. preservative

[0102] Phase III:

[0103] q.s. perfume oil

[0104] The ingredients were dissolved at 60° C., and then phase I wasadded to phase II. Phase III was added after cooling to 30° C.

[0105] A bleached strand of human hair (2 g) was treated with 0.5 g ofthe dyeing cream and left for 20 min. It was then rinsed with water,leaving hair dyeing as described in the dyeing example.

[0106] B) Hair Dyeing Lotion

[0107] 5 g of reactive dye of example 1

[0108]1.2 g of Natrosol® 250 HR (Aqualon/Hercules Inc. Wilmington, Del.,USA), (hydroxyethylcellulose to INCI)

[0109] 1 g of propylene glycol

[0110] ad 100 g of distilled water

[0111] q.s. preservative

[0112] A bleached strand of human hair (2 g) was treated with 0.5 g ofthe dyeing lotion and left for 20 min. It was then rinsed with water,leaving hair dyeing as described in the dyeing example.

[0113] C) Hair Dyeing Mousse

[0114] 2 g of reactive dye of example 1

[0115] 3 g of Luviskol® VA 64 (BASF Aktiengesellschaft, Ludwigshafen),(PVP/VA copolymer to INCI)

[0116] 0.45 g of ceteareth-25 (INCI)

[0117] 0.10 g of dimethicone (INCI)

[0118] 10 g of propane/butane

[0119] ad 100 g of distilled water

[0120] q.s. preservative

[0121] A bleached strand of human hair (2 g) was treated with 0.5 g ofthe hair dyeing mousse, left for 15 min and then rinsed with water. Aswell as being deeply colored, the hair was very easy to comb through andlooked cared-for. The hair dyeing obtained was as described in thedyeing example.

[0122] D) Hair Dyeing Shampoo

[0123] 5 g of reactive dye of example 1

[0124] 40 g of sodium laurylethersulfate to INCI (Texapon® N 28; HenkelKGaA, Düsseldorf)

[0125] 10 g of Tego® Betain L 7 (Goldschmidt AG/Degussa AG, Düsseldorf)(cocamidopropyl betaine to INCI)

[0126] 2 g of Gluatin WQ (wheat germ protein)

[0127] ad 100 g of distilled water

[0128] q.s. preservative

[0129] q.s. sodium chloride as thickener

[0130] The use of a hair dyeing shampoo makes it possible to combinecleaning and dyeing of the hair. A bleached strand of human hair (2 g)was treated with 0.5 g of the hair dyeing shampoo and rinsed out after 1min until the disappearance of foam. The hair dyeing obtained was asdescribed in the dyeing example.

[0131] E) Dyeing Paste

[0132] 2 g of reactive dye of example 1

[0133] 7 g of titanium dioxide

[0134] 15 g of Aerosil® (Degussa AG, Düisseldorf)

[0135] 10 g of Lutrol® F 127 (polyethylene glycol, BASFAktiengesellschaft, Ludwigshafen)

[0136] ad 100 g of distilled water

[0137] q.s. preservative

[0138] A bleached strand of human hair (2 g) was treated with 0.5 g ofthe hair dyeing paste, left for 15 min and then rinsed with water. Thehair dyeing obtained was as described in the dyeing example.

[0139] F) Hair Dyeing Shampoo

[0140] 10 g of reactive dye of example 1

[0141] 2.20 g of xanthan gum (Keltrol® T; Kelco Biopolymers, San Diego,Calif., USA)

[0142] 20.0 g of sodium laurylethersulfate

[0143] 2.50 g of olein diethanolamide

[0144] 0.10 g of Trilon® B (BASF Aktiengesellschaft, Ludwigshafen)

[0145] ad 100 g of distilled water

[0146] q.s. preservative

[0147] 25 g of the dyeing paste were suspended with 25 ml of distilledwater, a bleached strand of human hair (2 g) was treated with thisdyeing shampoo and left for 20 min. It was then rinsed out with water.The hair dyeing obtained was as described in the dyeing example.

[0148] G) Oxidative Hair Colouring Formulation

[0149] I. Dye cream emulsion weight % in use

[0150] q.s. water

[0151] 24.75 emulsion base

[0152] 4.0 reactive dye of example 1

[0153] 4.125 30% aqueous ammonium hydroxide

[0154] II. Emulsion base weight % in use

[0155] q.s. water

[0156] 1.5 ceteareth 25

[0157] 2.25 cetyl alcohol

[0158] 2.25 stearyl alcohol

[0159] 0.06 sodium benzoate

[0160] 0.07 phenoxyethanol

[0161] 0.08 benzyl alcohol

[0162] 0.02 tetrasodium EDTA

[0163] 2.0 silicone (DC Q2-8220 from Dow Corning)

[0164] III. Hydrogen peroxide emulsion base weight % in use

[0165] q.s. water

[0166] 4.2 ceteareth 25

[0167] 6.25 cetyl alcohol

[0168] 6.25 stearyl alcohol

[0169] IV. Hydrogen peroxide cream weight % in use

[0170] 36 hydrogenperoxide emulsion base

[0171] 17.7 35% hydrogen peroxide

[0172] q.s. water

[0173] The dye emulsion base is prepared by a one pot process asfollows:

[0174] 1. Add water to vessel. Heat to above the melt temperature of thefatty alcohols with agitation.

[0175] 2. Add fatty alcohols and any ethoxylated fatty alcohols, e.g.ceteareth-25, cetyl, stearyl and steareth-2, and allow to melt. Increaseagitation.

[0176] 3. Continue mixing with shear.

[0177] 4. Beginn cooling with shear adding preservatives at appropriatetemperature.

[0178] 5. During cooling add silicone with mixing until homogeneous.

[0179] 6. Cool to room temperature.

[0180] The hydrogen peroxide cream is also prepared similarly using aone pot process.

[0181] All 3 components are thoroughly mixed before application to hairfor a 30 minute period, followed by a rinsing with water and dried. Ahair colouration as described in the hair colouration example wasobtained.

We claim:
 1. Reactive dyes of the formula I

where R¹ to R⁴ are independently hydrogen, C₁₋C₈₋alkyl, C₂₋C₈₋alkyl,wherein nonadjacent CH₂ groups may be replaced by oxygen atoms or iminoor C₁₋C₄₋alkylimino groups and/or CH₂ groups by carbonyl groups,C₂-C₈-alkenyl, aryl, arylalkylene or a moiety containing a reactivegroup or the precursor of a reactive group, with the proviso that atleast one of R¹ to R⁴ is a moiety which contains a reactive group or theprecursor of a reactive group.
 2. Reactive dyes as claimed in claim 1,wherein the substituents independently have the following meanings: R¹and R²: hydrogen, C₁-C₄-alkyl; R³: hydrogen; R⁴: —M¹—SO₂—R⁵; M¹—(CH₂)_(n)—,

R⁵: vinyl, —CH₂—CH₂—OSO₃H, —CH₂—CH₂—O—C(═O)—R⁶, —CH₂₋CH₂₋O—R⁷; R⁶ andR⁷: C₁-C₆-alkyl; and n: 1 to
 4. 3. Reactive dyes as claimed in either ofclaims 1 and 2, wherein the substituents independently have thefollowing meanings: R¹ and R². hydrogen and methyl; R³: hydrogen; R⁴:—CH₂—CH₂—SO₂—CH═CH₂, —CH₂—CH₂—SO₂—CH₂—CH₂—OSO₃H.
 4. The use of reactivedyes defined as claimed in any of claims 1 to 3 for dyeing substratescontaining nucleophilic groups.
 5. The use of claim 4 for dyeingsubstrates containing hydroxyl, mercapto, amino and/or imino groups. 6.The use of either of claims 4 and 5 for dyeing keratinic fibers.
 7. Theuse of claim 6 for dyeing animal or human hair.
 8. Preparationscontaining at least one reactive dye defined as claimed in any one ofclaims 1 to
 3. 9. Preparations as claimed in claim 8, comprising haircosmetic products.